Process for preparing linear olefins

ABSTRACT

IN A PROCESS FOR PREPARING LINEAR OLEFINS WHICH COMPRISES POLYMERIZING AN ETHYLENE CONTAINING GAS IN THE PRESENCE OF A CATALYST COMPRISING THE REACTION PRODUCT OF A TRANSITION METAL HALIDE AND AN ALUMINUM ALKYL COMPOUND IN THE PRESENCE OF A DILUENT AND MAINTAINING THE MODE RATIO OF ETHYLENE TO OLEFIN REACTION PRODUCT AT A RELATIVELY HIGH LEVEL SO AS TO PRODUCE COMPRISING AT LEAST 90 MOLE PERCENT LINEAR OLEFINS, THE PROCESS IS IMPROVED AND THE PRODUCT PURITY IS MAINTAINED BY KILLING THE ACTIVITY OF THE CATALYST PRIOR TO THE OCCURENCE OF DELETERIOUS SIDE REACTION WHICH TENDS TO REDUCE THE PRODUCT PURITY.

United States Patent 3,662,021 PROCESS FOR PREPARING LINEAR OLEFINS Arthur W. Langer, .Ir., Watchung, N..ll., assignor to Esso Research and Engineering Company No Drawing. Continuation-impart of application Ser. No. 562,089, July 1, 1966, which is a continuation-impart of application Ser. No. 428,836, Jan. 28, 1965, which in turn is a continuation-in-part of application Ser. No. 55,845, Sept. 8, 1960, now Patent No. 3,168,588. ThlS application Dec. 13, 1968, Ser. No. 783,699 The portion of the term of the patent subsequent to Apr. 29, 1986, has been disclaimed Int. Cl. C07c 3/10 US. Cl. 260-68315 D 19 Claims ABSTRACT OF THE DISCLOSURE In a process for preparing linear olefins which comprises polymerizing an ethylene containing gas in the presence of a catalyst comprising the reaction product of a transition metal halide and an aluminum alkyl compound in the presence of a diluent and maintaining the mode ratio of ethylene to olefin reaction product at a relatively high level so as to produce a product comprising at least 90 mole percent linear olefins, the process is improved and the product purity is maintained by killing the activity of the catalyst prior to the occurrence of deleterious side reaction which tends to reduce the product purity.

CROSS REFERENCE This application is a continuation-in-part of Ser. No. 562,089, filed July 1, 1966 and now abandoned, which in turn is a continuation-in-part of Ser. No. 428,836, filed Jan. 28, 1965 and now abandoned, which in turn is a continuation-in-part of Ser. No. 55,845, filed Sept. 8, 1960 and now United States Pat. No. 3,168,588.

FIELD OF THE INVENTION This invention relates to an improved process for preparing linear olefins, particularly linear alpha olefins. More particularly, this invention relates to an improved process for polymerizing ethylene to obtain linear olefins having a number average molecular weight ranging from about 70 to 700. Still more particularly, this invention relates to an improved process for polymerizing ethylene to obtain a product comprising at least 90 mole percent linear alpha olefins having a number average molecular weight range of from about 70 to 700. Most particularly, this invention relates to an improved process for polymerizing ethylene to produce linear alpha olefins which comprises selectively terminating the polymerization reaction and inhibiting deleterious side reactions.

PRIOR ART It has been shown in the prior art (United States Pat. 2,993,942 and 2,907,805) that hydrocarbon lubricating oils having a molecular weight in the range of 80 to 2000 could be prepared by polymerizing ethylene with controlled catalyst, diluents and under controlled temperatures. The catalyst consisted of a transition metal halide and a halogenated aluminum alkyl compound. It has also been found that increased oil yields, catalyst reactivity, and improved molecular weight control could be obtained by the addition of a minor amount of a lower alkanol, as

3,662,021 Patented May 9, 1972 'ice a catalyst modifier to the reaction system. Both the modified and unmodified systems described above resulted, under the conditions in the reaction, in the production of major portions of olefins other than linear alpha olefin products, particularly C=CH2 and It has now been discovered that the polymerization of ethylene under controlled conditions to produce linear olefins can be made selective for linear alpha olefins by terminating the reaction by the addition of an agent or agents to kill the activity of the catalyst and prevent deleterious side reactions. It has been found that the termination of the reaction by adding conventional catalyst killing agents, e.g., alcohol or water results in a product other than one comprising at least 90 mole percent linear alpha olefins. The process of this invention requires the termination of the ethylene polymerization reaction by the addition of specificc agents under specific conditions. The ethylene polymerization reaction comprises a sequence of critical reaction variables comprising, inter alia, a mole ratio of ethylene to product, use of a particular soluble catalyst, ethylene pressure, and product olefin concentration.

R Type II (R CH=CHR), Type III SUMMARY OF THE INVENTION In accordance with this invention, therefore, an improved process for preparing linear olefins, particularly linear alpha olefins, is provided which comprises polymerizing ethylene or an ethylene containing gas in the presence of a substantially soluble catalyst comprising the reaction product of a transition metal halide, the transition metal being selected from the group consisting of reducible heavy metals of Groups IV-B to VI-B and VIII with an aluminum alkyl compound such that the ultimate formula of the aluminum alkly compound is AlR X wherein n is less than 2, R is a hydrocarbyl radical, and X is a halogen, conducting the polymerization reaction in presence of a suitable diluent, at temperatures below about C. and ethylene pressures above about 50 p.s.i.a., maintaining the mole ratio of ethylene to olefin reaction product above about 0.8 throughout the reaction, and killing catalyst activity after at least about 5 Wt. percent, based on diluent, of product olefin has formed by adding an agent or agents to kill the polymerization activity of the catalyst and preventing or inhibiting deleterious side reactions. In an embodiment of this invention a polymerization killing agent is added and another agent, designed to prevent or inhibit side reactions, e.g., isomerization, is added either before, after or simultaneously with the polymerization killing agent. In another embodiment of this invention a single agent can be added to the reaction mixture to accomplish both results, i.e., kill polymerization activity and inhibit deleterious side reactions. In yet another, and preferred embodiment, the polymerization killing agent is added to the reaction mixture prior to the removal of the ethylene from the reaction mixture. Generally, however, the agent or agents added to the reaction mixture are added under relatively critical conditions.

The reaction can be terminated either by removing the ethylene containing gas thereby stopping the polym erization; or, by adding the polymerization catalyst killing agent, thereby stopping the polymerization activity of the catalyst.

While not wishing to be bound by any particular theory, it is believed that the catalysts employed herein as ethylene polymerization catalysts tend also to promote the copolymerization of the product olefins formed by the reaction. Now since the object of this invention is to produce and maintain a product comprising at least 90 mole percent linear olefins, it is obvious that copolymerization of the reaction product will lead to increased formation of branched products at the expense of linear products. Consequently, the reaction must be terminated at a suitable point where an economically feasible product yield has been obtained but prior to the occurrence of copolymerization to the extent that it reduces product purity to a level below about 90 mole percent linear olefins. While generally conventional polymerization killing agents can be added to the reaction mixture to terminate the polymerization activity of the catalyst, e.g., water, alcohols, acids, etc., such agents tend to protonate the catalyst and turn it into a strongly acidic Friedel-Crafts catalyst. A Friedel-Crafts catalyst in the reaction mixture, however, promotes isomerizations, alkylations, carbonium ion polymerizations, etc., which are deleterious in that such side reactions reduce the linearity of the reaction product. Consequently, it is often-times necessary to add an additional agent, i.e., a base, to the reaction mixture to neutralize the Friedel- Crafts activity of the catalyst.

Generally, catalyst atcivity may be killed before or after the ethylene is removed from the reaction mixture. When the catalytic activity is killed after ethylene removal the polymerization killing agent must be added within about one minute after ethylene removal. This is a critical variable in the preservation of the linear olefin reaction product. Thus, as previously mentioned, the polymerization catalyst also promotes copolymerization of the product olefin. However copolymerization is inhibited due to the relatively high mole ratio of ethylene to product olefin maintained throughout the reaction. (This ratio is maintained by the high ethylene pressure, i.e., above about 50 p.'s.i.a. ethylene, in the reaction mixture which promotes ethylene polymerization activity rather than copolymerization.) When the ethylene has been re moved the selectivity to ethylene polymerization is lost and copolymerization will be promoted. In order to prevent copolymerization from destroying the linear product it is critical that the polymerization activity of the catalyst be killed within about one minute of ethylene removal. After killing the polymerization activity with a conventional agent, the Friedel-Crafts activity must be neutralized, also within a critical period. Thus, side reactions due to the presence of an acidic catalyst can also destroy the linear reaction product. The base, or neutralizing agent, must then be added within about one minute after the polymerization activity is killed.

Of course, this invention contemplates the addition of the base prior to the addition of the polymerization killing agent. Nevertheless, polymerization activity must be killed within about one minute of ethylene removal. Thus, if the base is added one minute after ethylene removal, the polymerization killing agent must be added simultaneously. However, the base may be added within about two minutes after ethylene removal if the polymerization killing agent is first added about one minute after ethylene removal.

The foregoing critical relationships hold where the reaction is terminated at ambient temperatures, i.e., room temperatures of about l825 C., and above. It will be obvious to those skilled in the art that if the temperature of the reaction mixture is reduced, i.e., taken below room temperature, after the polymerization activity is killed,

addition of the base can be delayed somewhat. Of course, the lower the temperature of the reaction mixture, the longer base addition can be delayed. Using the very general rule that reaction rate doubles or halves with each 10 C. change in tempeature, a rough guide can be established and the period during which the base must be added (to prevent undue isomerizations, alkylations, etc.) can be readily found by simple experimentation.

Thus, the general rule is that the polymerization activity of the catalyst be killed within about one minute after termination of the reaction. It is preferred, however, to add the polymerization killing agent prior to the termination of the reaction, i.e., before the ethylene is flashed otf, a point which is obviously within the general period just stated. This procedure eliminates observance of the critical period when the reaction is terminated prior to killing polymerization activity. Additionally, the critical period for base addition is also obviated since the reaction mixture will be auto refrigerated due to flashing the ethylene, e.g., the temperature can be reduced to below l0 C. by auto refrigeration. Furthermore, at reduced temperatures the catalyst can be washed out thereby eliminating the acid function and obviating the need for a neutralizing agent.

Some typical polymerization killing agents are water; alcohols, both mono and poly hydroxylic, cyclic and acyclic, aliphatic and aromatic; carboxylic acids, phenols, etc. The organic compounds Which can be used are those having from 1 to 15 carbon atoms, the lower carbon number inexpensive compounds being preferred. Thus alcohols and acids having from 1 to 8 carbons are preferred, with 1 to 4 carbons being most preferred. Examples of the most preferred killing agents include water, methanol, ethanol, isopropanol, t-butanol, and ethylene glycol.

Bases that can be employed to neutralize Friedel-Crafts activity can be any base that will elfectively neutralize this acid function. Generally, such bases can be broadly characterized as Lewis bases. Such materials which can be used in the practice of this invention include caustics such as alkali metal and alkaline earth metal hydroxides and carbonates, ammonium hydroxide and quaternary ammonium bases and organic bases such as ethers and organic nitrogen compounds, e.g., amines and cyclic nitrogen bases. As specific examples, there can be named lithium hydroxide, sodium hydroxide, potassium carbonate, magnesium hydroxide, calcium carbonate, tetramethyl ammonium hydroxide, tetrahydrofuran, ammonia, C C aliphatic amines, e.g., ethylamine and methylamine, aniline, p-toluidine and heterocyclic nitrogen compounds, e.g., pyridine. These bases may be used alone, in mixtures or dissolved in solvents such as water, alcohols, glycols, etc. The preferred bases are sodium hydroxide or ammonia dissolved in Water or alcohols. Although larger amounts may be used, it is desirable to use 0.5 to 2 moles of base per atom of halogen in the catalyst, preferably about stoichiometric amounts. It is obvious that a base such as sodium hydroxide dissolved in water or alcohols serves to kill polymerization activity simultaneously with neutralization. Lewis bases kill polymerization activity by complexing more strongly than alpha olefins with the transition metal site. On the other hand, protonic agents kill polymerization activity by destroying the metal-carbon bonds of the catalyst. Thus, a base is needed in addition to the protonic agents to neutralize the Friedel-Crafts activity of the catalyst residues, whereas a Lewis base such as triethylamine inactivates both types of catalyst activity.

The catalyst which can be used is a complex reaction product which is substantially soluble in the polymerization system and is obtained by partially reacting a reducible, heavy transition metal halide of selected Group IV-B to VI-B or VIII metal with an aluminum alkyl compound such that the ultimate formula of the aluminum alkyl compound is AlR X wherein n is less than 2, 'R is alkyl, cycloalkyl or aralkyl, preferably containing 1 to 20 carbon atoms, for example, methyl, ethyl, isobutyl, cyclohexyl, benzyl, etc., and X is Cl or Br or I. While most transition metal halides are suitable components of the catalyst complex, when the desired product is the branched chain olefins of the prior art, it has been found that compounds such as VCL, and FeCl are unsuitable for the preparation of linear alpha-olefins. The preferred transition metal catalyst component is a titanium compound having a valency of 3 or 4, preferably 4, and may be represented by the formula: TiX A wherein a=3 or 4, b= or 1 and a+b=3 or 4, X=Cl or Br and A is C1 or Br or an anion derived from a protonic compound such as an alcohol (ROH) or a carboxylic acid (RCOOH). The R of the protonic compound may be an alkyl, aryl, aralkyl or cycloalkyl group. The TiX A component may be made in situ by reacting TiX with the protonic compound. Thus, the preferred transition metal component of this invention may be selected from the group TiX TiX OR' and TiX OOCR'. Typical examples of such compounds are TiCl TiBr TiX OC H and TiX OOCCH As set forth above, it is essential that the aluminum alkyl catalyst after reaction with the transition metal halide have the formula AlR X The molar ratio of alkyl aluminum halide to the transition metal halide is not critical to this invention as long as the AlR,,X reaction product has the proper formula. The ratio may be 0.1/1 to 150/ 1 or more. Catalyst concentration is normally in the range of 0.1 to grams per liter of diluent.

Catalyst polymerization activity can be enhanced and product molecular weight may be controlled by the addition of small amounts of alcohols. The alcohols which can be used in the practice of this invention are those having from 1 to carbon atoms, preferably those having from 1 to 8 carbons, and most preferably those alcohols having 1 to 4 carbon atoms. Thus, the alcohols that can be used include methanol, ethanol, n-propanol, isopropanol, n-butanol, secbutanol, tertiary butanol, isobutanol and all of the C and C alcohols. C to C diols in which the hydroxy groups are not attached to adjacent carbon atoms are also useful. Especially preferred and desirable are: tertiary butanol, secondary butanol, isoor n-butanol, and iso-propanol. These alkanols are utilized in a minor amount, i.e. so that the ratio of ROH/R (based on aluminum alkyl) after alkylation or reduction of the transition metal is not greater than 0.5.

Ethylene is unique in the instant invention in that other olefins do not respond to give linear alpha-olefins. Therefore, it is desirable to use essentially pure ethylene or mixtures of ethylene with inert gases as the feed for the process of this invention. Ethylene feeds containing minor amounts of other olefins may be used provided that the extent of copolymerization does not decrease product linearity below 90%.

Polymerization diluent is not a critical feature of this invention. The useable diluents are aromatic hydrocarbon and haloaromatic solvents as well as aliphatics and naphthenics. Less preferred solvents are halogenated aliphatic compounds which, while capable of being employed in the process of preparing linear alpha-olefins, require the utilization of higher pressures to achieve average molecular weights of the same order as the preferred solvents. The preferred diluents include halogenated aromatics such as chlorobenzene, dichlorobenzene, chlorotoluene, etc., and aromatics such as benzene, toluene, xylene, tetrahydronaphthalene, etc., aliphatics such as pentane, heptane, iso-octane, etc., and naphthenes such as cyclohexane, methylcyclohexane, decahydronaphthalene, etc. The suitable halogenated aliphatic diluents include methyl chloride, ethyl chloride, dichloromethane, etc. Mixtures of these diluents may be used. Also, mixtures of the above types with aliphatic or naphthenic solvents may be used. The diluent or diluent mixture may be used to control the product molecular weight distribution to obtain maximum selectivity to the desired olefin products.

The prior art obtained highly branched olefins (60%) when using the closely related catalyst and diluent systems at pressures of 7 to 30 p.s.i.g., e.g., British Pat. 874,577. Ethylene pressures above 50 p.s.i.a. are essential for making linear olefins in high selectivities. Although some variations are permitted depending upon the catalyst composition, diluent and temperature, the preferred pressures are above about to 100 p.s.i.a. in order to produce commercially attractive yields (at least above 5 weight percent and preferably above 10 weight percent olefins in the reactor effluent) of linear alpha-olefins having a purity greater than about mole percent. The most preferred range is above p.s.i.a. ethylene pressure. At very high ethylene pressures the process may become uneconomical because of the equipment requirements and ethylene recycle. Nevertheless, higher pressures tend to increase the selectivity of the reaction to linear alpha olefins.

The ratio of moles of ethylene to the moles of products throughout the reaction and insured by the ethylene pressures referred to above, must be above about 0.8 in order to effect the selective synthesis of linear olefins from ethylene and inhibit copolymerization effects. The preferred ratio of ethylene to products is above about 2.0. The upper limit of the mole ratio of ethylene to product is not critical. The mole ratio of ethylene to product must be'above 0.8 or the product formed contains more than 10% branched chain olefins at product concentrations required to obtain commercially attractive yields.

The catalyst of this invention enables the process for making linear-alpha-olefins to be carried out at temperatures below +75 0, preferably between about -30 C. and about +50 C. The selection of a particular temperature will permit control of the average number molecular weight of the product.

Reaction times are not particularly critical when operating under the preferred conditions and they will normally be in the range of 0.1 to 5 hours to obtain product concentrations greater than 5% by weight in the diluent. The process may be carried out in batch or continuous operation. However, high product purity and high concentration are achieved most easily in batch reactions or in continuous systems operating under essentially plug flow conditions. A reactor may consist of a long pipe through which the diluent and catalyst flo-w with ethylene being introduced at many points along the pipe to maintain the desired ethylene concentration. In such a system monomer concentration need not be constant but may be controlled differently in different sections of the reactor to achieve the best balance of activity, molecular weight and product purity. Stirred tank reactors may be operated in series to approach plug flow.

After the catalyst has been effectively neutralized, the residues may be removed from the products in any conventional way, such as washing with water or aqueous caustic, adsorption, ion exchange resins, etc. If the catalyst has been neutralized according to this invention, the products may be distilled directly from the catalyst residues without decreasing product purity. However, it is preferred to remove the residues before distillation in order to minimize deposits in the distillation towers.

Based on the teachings of this invention to destroy both polymerization and Friedel-Crafts activity to permit isolation of greater than 90% pure linear alpha-olefins, it is clearly within the scope of the invention to accomplish the same results by alternatives such as rapid solvent extraction or solid adsorption techniques, particularly if these are used before all of the ethylene has been flashed. However, such techniques are generally less effective than the preferred neutralization procedure.

The following examples are submitted in order to more particularly point out applicants invention but are not to be construed as limitations upon the scope of the instant invention as described in the appended claims.

EXAMPLE 1 A series of runs were made to determine the effect of ethylene pressure on product linearity. All were carried out at 20 C. using 500 ml. of either chlorobenzene or xylene diluent. The proportions of catalyst components were maintained constant, although total catalyst concentration was varied by a factor of four. The TiCl in 400 ml. diluent was added to the reactor under dry nitrogen and cooled to 20 C. The t-butyl alcohol and AlEt Cl were mixed 5 minutes in 100 ml. diluent before adding the AlEtCl The latter was added to the reactor and the total mixture allowed to react minutes at C. High purity ethylene was obtained by passing commercial C.P. ethylene over copper oxide at 205 C. to remove oxygen and then through 3A molecular sieves to remove water. It was stored in a one-gallon reservoir at 100 p.s.i.g. After the catalyst pretreatment, the reactor contents were subjected to high speed stirring. Ethylene was added as necessary to maintain pressure and the temperature was kept at 20 C. by circulating coolant through coils around the reactor.

The results are summarized in Table I. After killing the catalyst with about to 50 m1. methanol containing NaOH, the product was water-washed twice and dried over K CO The products were analyzed quantitatively for olefin types by infrared, and the split between linear and branched products was determined by quantitative gas chromatography on a sample of total reactor product. Using a four-foot column of silicone gum rubber and tem perature programming, it was possible to obtain the yield of each product up to C H Product linearity is expressed as mole percent in the C124 fraction. It was compared on the C1240 cuts because this was the most accurate analysis considering volatility losses from C and G. C. resolution of the branched and linear olefins above C The linearity of the total product is much higher than that shown for the C1240 fraction because in all pressure runs the C fraction is essentially 100% linear, and it is a major portion of the total product.

As shown in Table I, the selectivity to linear alphaolefins increases sharply above about 50 p.s.i.a. and becomes greater than 90% above about 100 p.s.ia At still higher ethylene pressures, selectivity rapidly approaches 100% in the C1240 fraction. Excellent results were obtained with either chlorobenzene or xylene diluent. In addition to the effect on olefin linearity, ethylene pressure may be used together with catalyst composition, solvent polarity and polymerization temperature to control the product molecular Weigh. As shown in Table I for chlorobenzene diluent, the number average molecular weight increased from 98.8 at atmospheric pressure to 147 at 500 p.s.i.a.

8 1 ml. of 1 M NaOH in methanol. The second hour sample (18 ml.) was pressured from the reactor directly into a vessel containing the 1 ml. of 1 M NaOH in order to kill the catalyst immediately. The amount of NaOH was taken to be approximately equivalent to the chloride content of the catalyst in the sample.

Alkylation took place so extensively in the first hour sample that it was impossible to do the usual analysis. Product concentration was estimated to be about 30 to 40 weight percent. No linear alpha-olefins were indicated by infrared analysis. The product was predominantly alkylated xylene.

The second hour sample was 96.9% linear alpha-olefins despite the fact that product concentration was much higher (53.6 weight percent). By analogy with all other experiments, the first hour sample should have had the highest linearity; in this case, an estimated 98 to 99% if the catalyst had been destroyed immediately after flashing ethylene.

This example illustrates that high purity olefins can only be obtained by rapid destruction of the catalyst activity after flashing ethylene.

EXAMPLE 3 A catalyst solution was prepared by reacting l2 mmoles AlEt Cl and 2 mmoles t-butanol in ml. chlorobenzene for 5 minutes, then adding 12 mmoles AlEtCl 400 ml. chlorobenzene containing 2 moles TiCl was charged to the reactor, cooled to -20 C., the aluminum alkyl solution was added, and the catalyst was pretreated 15 minutes at 20 C. Ethylene was charged to p.s.i.a. and polymerization was continued one hour at 150 to p.s.i.a. and 20 C.

The total reactor product was flashed into 100 ml. methanol without any base present. After filtering off 4.8 'grams Wax, the filtrate was water-washed, dried over K CO and distilled using a 15 plate O'ldershaw column at 20/ 1 reflux ratio. Infrared analysis of the C C cut gave only 80% linear alpha-olefins and 20% internal olefins (Type II-trans). Since some Type II-cis olefins would have been produced simultaneously by isomerization, the linear alpha-olefin purity was considerably less than 80%.

Experiments in which the products were flashed into methanol plus NaOH gave over 98% pure linear alphaolefins. In the infrared analyses of these samples, the Type II-trans absorption at 10.3 was barely discernible.

This example illustrates that rapid quenching of the Catalyst: AlEt Cl/AlEtOI /TiCV/t-BuO H.

b Gaseous ethylene bubbled continuously through diluent at atmospheric pressure.

a Number average molecular weight of total olefin product.

EXAMPLE 2 A catalyst solution containing 1.5 mmoles AlEt Cl, 3.0 mmoles AlEtCl and 3.0 mmoles TiCL; in 250 ml. xylene was pretreated 30 minutes at 15 C., cooled to 0 C. and ethylene added rapidly. Polymerization was carried out two hours at 0 C. and 520 p.s.i.a ethylene pressure. Samples of the total reactor product were taken hourly and analyzed as in Example 1.

In taking the reactor samples, the ethylene is allowed to flash off at atmospheric pressure, thereby refrigerating the sample. The first hour sample (10 ml.) was allowed to stand 15 minutes before killing the catalyst with catalyst polymerization activity is not sufiicient to obain high purity alpha-olefins, In the absence of a base, double bond isomerization occurs to produce the less desirable internal olefins. It shows that it is critical to destroy the Friedel-Crafts activity of the catalyst as well as the polymerization activity. Besides double bond isomerization, residual catalyst Friedel-Crafts activity could also cause alkylation and cationic polymerizations which would further decrease the alpha-olefin purity.

With high polymers any residual polymerization or Friedel-Crafts activity has a negligible effect, if any, on product properties. In a process for making linear alphaolefins, however, it is critical to destroy or neutralize both types of catalyst activity.

EXAMPLE 4 Following the procedure of Example 3 but terminating the polymerization with 10 ml. methanol plus 10 ml. 6NNH OH prevented isomerization and preserved the alpha-olefin purity.

EXAMPLE 5 A series of runs were made to determine the eifect of quenching various catalyst composititons. The reaction conditions are set forth in Table II. In each run the reaction was quenched with a mixture of methanol and NaOH. It is to be seen from Table II that the instant process resulted in a highly linear product.

TABLE II Run l 2 3 4 AlEtClz, mmoles 5 2 5 0. 5 A1013, mmoles 0 0.2 0 TiCh, rmnoles 1 1 0.05 1 Solvent, rnl.:

Xylene. 125

CH5CL. 250 250 Pretreat, C./m.1n 50/30 50/30 50/30 Al/Ti, mole ratio 5 104 0.5 Et/Al, ratio 8 0. 8 0.5 0.95 0 Polymerization:

Temp, C 15 50 50 50 02114, p.s.i.a.... 400 400 200 400 Time, hrs 1 1 3 0. 5 Results:

Yield, g3 132 92 23 51 Linearity, mole percent s 91. 5 91. 2 95. 2 94. 3

8 Assuming mono-alkylation of 'IiOl4. b Excluding 20% losses during work-up. Determined on Cir-2o fraction.

What is claimed is:

1. In a process for selectively preparing linear olefins having a number average molecular weight ranging from about 70 to about 700, wherein an ethylene-containing gas is polymerized in the presence of a substantially soluble catalyst comprising the reaction product of a titanium compound selected from the group consisting of TiX TiX 0R', TiX OOCR wherein X is selected from the group consisting of chlorine and bromine and R is selected from the group consisting of alkyl, aryl, aralkyl and cycloalkyl and an aluminum alkyl compound such that the ultimate formula of the aluminum alkyl compound is AlR,,X' wherein R is selected from the group consisting of alkyl, aralkyl and cycloalkyl, X is selected from the group consisting of chlorine, bromine and iodine and n is less than 2, in the presence of a diluent and at a temperature of less than about 75 C. and an ethylene pressure above about 50 p.s.i.a., wherein the mole ratio of ethylene to reaction product is maintained above about 0.8 throughout the reaction, an improvement therewith which comprises the step of adding catalyst killing agent and a Lewis base to the reaction mixture after the 'formation of about 5 weight percent of olefin product and within about one minute after the ethylene-containing gas has been removed from the reaction mixture, whereby deleterious side reactions are prevented and a reaction product comprising at least about 90 mole percent linear alpha olefins is preserved.

2. The process of claim 1 wherein the catalyst killing agent is selected from the group consisting of water, alcohols and carboxylic acids.

3. The process of claim 1 wherein said Lewis base is added to the reaction mixture after the catalyst killing agent is added to the reaction mixture.

4. The process of claim 1 wherein the Lewis base and the catalyst killing agent are added simultaneously to the reaction mixture.

5. The process of claim 4 wherein the Lewis base is sodium hydroxide and the catalyst killing compound is methanol.

6. The process of claim 1 wherein the Lewis base is 10 added to the reaction mixture prior to the catalyst killing agent.

7. The process of claim 3 wherein the Lewis base is selected from the group consisting of alkali metal hydroxides and carbonates, alkaline earth metal hydroxides and carbonates and ammonium hydroxide.

8. The process of claim 7 wherein the Lewis base is an amine.

9. The process of claim 8 wherein the Lewis base is triethylamine and is the only agent added to the reaction mixture.

10. A process according to claim 3 wherein the Lewis base is a quaternary ammonium base.

11. A process according to claim 3 wherein the Lewis base is an organic nitrogen compound.

12. In a process for preparing a reaction product comprising at least about mole percent linear alpha-olefins having a number average molecular weight ranging from about 70 to about 700 which comprises polymerizing an ethylene containing gas in the presence of a substantially soluble catalyst comprising the reaction product of a titanium halide selected from the group consisting of TiX TiX OR, TiX O0CR, wherein X is selected from the group consisting of chlorine and bromine and R is selected from the group consisting of alkyl, aryl, aralkyl, and cycloalkyl; and an aluminum alkyl compound such that the ultimate formula of the aluminum alkyl compound is AlR X' wherein R is selected from the group consisting of alkyl, aralkyl, and cycloalkyl, X is selected from the group consisting of chlorine, bromine and iodine, and n is less than 2; in the presence of diluent, at a temperature of less than about 75 C., and an ethylene pressure above about 50 p.s.i.a. wherein the mole ratio of ethylene to olefin reaction product is above about 0.8 throughout the reaction, the improvement which comprises terminating the reaction by adding to the reaction mixture prior to the removal of the ethylene containing gas and after above about 5 wt. percent of olefin reaction product has formed, a polymerization catalyst killing agent thereby preserving a reaction product comprising at least about 90 mole percent linear alpha-olefins and removing the catalyst residues from said reaction mixture.

13. The process of claim 12 wherein the catalyst killing agent is selected from the group consisting of water, alcohols, and carboxylic acids.

14. The process of claim 13 wherein a Lewis base is added to the reaction mixture not later than about one minute after the catalyst killing agent is added.

15. The process of claim 15 wherein the Lewis base is selected from the group consisting of alkali metal hydroxides and carbonates, alkaline earth metal hydroxides and carbonates and ammonium hydroxide.

16. The process of claim 14 wherein the catalyst killing agent and the Lewis base are added to the reaction mixture simultaneously.

17. The process of claim 14 wherein the Lewis base is added to the reaction mixture prior to the addition of the catalyst killing agent.

18. The process of claim 14 wherein the Lewis base is sodium hydroxide and the catalyst killing agent is methanol.

19. The process of claim 14 wherein the Lewis base is ammonium hydroxide.

References Cited UNITED STATES PATENTS 2,907,805 10/1959 Bestian et al. 260683.15

3,108,145 10/1963 Antonsen 260683.15

3,441,630 4/1969 Langer et al. 260-683.15

FOREIGN PATENTS 874,577 8/ 1961 Great Britain 260-68315 PAUL M. COUGHLAN, 1a., Primary Examiner 

